Poly(alkylene ether) amines having a hydroxy(oxypropylene) connecting group

ABSTRACT

Poly(alkylene ether) amines having the formula: ##STR1## wherein A is an amine moiety having at least one basic nitrogen atom; R 1  is a hydrocarbyl group having a sufficient number of carbon atoms to render the poly(vinyl ether) amine soluble in hydrocarbons boiling in the gasoline or diesel fuel range; R 2  is an alkylene group having 2 to about 8 carbon atoms; R 3 , R 4 , R 5 , R 6 , R 7  and R 8  are each independently hydrogen or a lower alkyl group having 1 to about 4 carbon atoms; R 9  is an alkyl group having 1 to about 10 carbon atoms; m is 0 or 1; n is an integer from 5 to 99; and W is a hydroxy(oxypropylene) group having the formula: ##STR2## or mixtures thereof. The poly(vinyl ether) amines of formula I are useful as fuel additives for the prevention and control of engine deposits.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel end-functionalized poly(vinyl ethers).More particularly, this invention relates to novel poly(vinyl ether)amines having a hydroxy(oxypropylene) connecting group and their use infuel compositions to prevent and control engine deposits.

2. Description of the Related Art

It is well known that automobile engines tend to form deposits on thesurface of engine components, such as carburetor ports, throttle bodies,fuel injectors, intake ports and intake valves, due to the oxidation andpolymerization of hydrocarbon fuel. These deposits, even when present inrelatively minor amounts, often cause noticeable driveability problems,such as stalling and poor acceleration. Moreover, engine deposits cansignificantly increase an automobile's fuel consumption and productionof exhaust pollutants. Therefore, the development of effective fueldetergents or "deposit control" additives to prevent or control suchdeposits is of considerable importance and numerous such materials areknown in the art.

Deposit control additives, however, differ in their effectiveness forpreventing or controlling deposits on various engine components. This isbelieved to be due primarily to the fact that each engine component hasa different operating temperature and some deposit control additives arenot sufficiently stable on the surface of certain engine components toperform their intended function. In this regard, deposits on intakevalves are particularly difficult to control, since intake valveoperating temperatures can exceed 300° C. At such high temperatures,many fuel additives are too volatile to be effective, while othersthermally decompose.

Therefore, it would be particularly desirable to provide effectivedeposit control additives which have improved thermal stability atnormal engine intake valve operating temperatures and which further havea sufficient molecular weight so as to be nonvolatile at suchtemperatures. The present invention discloses a new class of poly(vinylether) amine fuel additives having such properties.

Polyether fuel additives are well known in the art. These prior artadditives, however, have a poly(oxyalkylene) "backbone", i.e. thepolyether portion of the molecule consists of repeating oxyalkyleneunits, i.e. [--CHR--CHR--O--_(x). In contrast, the fuel additives of thepresent invention have a vinyl ether polymer backbone consisting ofrepeating vinyl ether units, i.e. [--CHR--CR(OR)--]_(x). U.S. Pat. No.4,261,704, issued Apr. 14, 1981 to W. K. Langdon, for example, disclosesa poly(oxyalkylene) polyamine prepared by first reacting apoly(oxyalkylene) polyol or a poly(oxyalkylene) glycol monoether with ahalogen-containing compound, such as an epihalohydrin. The resultinghalogenated ether is then aminated by reaction with a mono- orpolyamine. The resulting mono- or polyamine derivatives are taught to beuseful as intermediates for preparing cationic surfactants, cationicpolymers and as fuel detergent additives.

Similar poly(oxyalkylene) polyamines, prepared using an epihalohydrin,are described in U.S. Pat. No. 4,281,199, issued Jul. 28, 1981 to W. K.Langdon. The compounds described in each of the aforementioned patentshave a poly(oxyalkylene) backbone.

Other fuel additive compositions having a connecting group derived froman epihalohydrin are known. For example, U.S. Pat. No. 4,975,096, issuedDec. 4, 1990 to T. F. Buckley, discloses long chain aliphatichydrocarbyl amines having a long chain aliphatic hydrocarbyl componentand an amine component connected by an oxy-alkylene hydroxy connectinggroup. These compounds are taught to be useful as deposit controladditives in fuel compositions and as dispersants in lubricating oilcompositions. Similar multipurpose additives for hydrocarbon fuels andlubricating oils, prepared from substituted phenols, epichlorohydrin andamines, are described in U.S. Pat. No. 4,134,846, issued Jan. 16, 1979to W. H. Machleder et al. The deposit control additives described inthese patents do not have a polyether backbone.

End-functionalized poly(vinyl ethers) are also known in the art. Forexample, A. Verma et al. in Polymer Preprints, 1991, 32, 322, describethe synthesis and characterization of functionalized poly(butyl vinylether) oligomers having an aldehyde or a primary hydroxyl endgroup.These poly(vinyl ethers) are prepared by the living polymerization ofbutyl vinyl ether using a hydrogen iodide/zinc iodide initiating system.The polymerization reaction is terminated with aqueous potassiumcarbonate to form the aldehyde endgroup, which can subsequently bereduced to form the primary hydroxyl endgroup. Poly(vinyl ethers) havingamine end-groups are also known. C. G. Cho et al., Polymer Preprints,1987, 28, 356, describe the synthesis of amine-terminated poly(alkylvinyl ethers) by quenching the living polymerization of alkyl vinylethers with p-methyl styrene and an amine. The resulting poly(alkylvinyl ether) is covalently linked to the amine through a p-methylstyrenic unit. M. Miyamoto et al., Macromolecules, 1985, 18, 123,describe the synthesis of poly(vinyl ethers) having a terminal aminegroup by quenching the living polymerization reaction of vinyl ethermonomers with aliphatic amines. The resulting poly(vinyl ether) amineshave an α-amino ether endgroup. Similarly, M. Sawamoto et al., PolymerBulletin, 1987, 18, 117, describes quenching vinyl ether polymerizationreactions with anilines to form aniline-terminated poly(vinyl ethers).

Amine-terminated poly(isobutyl vinyl ethers) having a primary amine atthe beginning of the vinyl ether polymer are described by T. Hashimotoet al. in J. Poly. Sci. Polym. Chem. Ed., 1990, 28, 1137. Thesepoly(vinyl ethers) are prepared by initiating the living polymerizationof isobutyl vinyl ether with 2-(vinyloxy)ethyl phthalimide. Thephthalimide group is then removed with hydrazine to produce apoly(isobutyl vinyl ether) having a 2-aminoethyl ether moiety on thefirst vinyl ether unit of the polymer.

It has now been discovered that the thermal stability of polyether fueladditives can be substantially improved by replacing thepoly(oxyalkylene) component of such additives with a poly(vinyl ether)component. The resulting poly(vinyl ether) amines are surprisinglyeffective for controlling fuel system deposits, particularly intakevalve deposits.

SUMMARY OF THE INVENTION

The present invention provides novel poly(vinyl ether) amine fueladditives which are useful for the prevention and control of enginedeposits, particularly intake valve deposits.

The poly(vinyl ether) amines of the present invention have the formula:##STR3## wherein A is an amine moiety having at least one basic nitrogenatom; R₁ is a hydrocarbyl group having a sufficient number of carbonatoms to render the poly(vinyl ether) amine soluble in hydrocarbonsboiling in the gasoline or diesel fuel range; R₂ is an alkylene grouphaving 2 to about 8 carbon atoms; R₃, R₄, R₅, R₆, R₇ and R₈ are eachindependently hydrogen or a lower alkyl group having 1 to about 4 carbonatoms; R₉ is an alkyl group having 1 to about 10 carbon atoms; m is 0 or1; n is an integer from 5 to 99; and W is a hydroxy(oxypropylene) grouphaving the formula: ##STR4## or mixtures thereof.

The present invention further provides a fuel composition comprising amajor amount of hydrocarbons boiling in the gasoline or diesel range andan effective deposit-controlling amount of a poly(vinyl ether) amine ofthe present invention.

The present invention additionally provides a fuel concentratecomprising an inert stable oleophilic organic solvent boiling in therange of from about 150° F. to 400° F. and from about 10 to 70 weightpercent of a poly(vinyl ether) amine of the present invention.

The present invention also provides a method for reducing enginedeposits in an internal combustion engine comprising operating theengine with the aforementioned fuel composition containing an effectivedeposit-controlling amount of a poly(vinyl ether) amine of the presentinvention.

Among other factors, the present invention is based on the surprisingdiscovery that fuel additives having a poly(vinyl ether) backbone haveimproved thermal stability and provide superior control of deposits,particularly on intake valves.

DETAILED DESCRIPTION OF THE INVENTION

The fuel additives provided by the present invention have the generalformula: ##STR5## wherein A, R₁ -R₈, W, m and n are as definedhereinabove.

A is preferably an amine moiety derived from ammonia, a monoamine having1 to about 8 carbon atoms, or a polyamine containing 2 to about 12 aminenitrogen atoms and from 2 to about 40 carbon atoms. More preferably, Ais an amine moiety derived from ammonia or a polyalkylene polyaminecontaining 2 to about 12 nitrogen atoms and 2 to about 24 carbon atoms.Still more preferably, A is a polyamine moiety derived from apolyalkylene polyamine having the formula:

    H.sub.2 N--(R.sub.10 NH).sub.y --H

wherein R₁₀ is alkylene having 2 to about 6 carbon atoms and y is aninteger from 1 to 3.

Preferably, R₁ is a hydrocarbyl group having at least 5 carbon atoms.More preferably, R₁ is a hydrocarbyl group having about 8 to about 120carbon atoms. In a particularly preferred embodiment of the presentinvention, R₁ is alkyl having 8 to about 120 carbon atoms or alkylphenylhaving an alkyl group containing 4 to about 100 carbon atoms. Morepreferably, R₁ is alkyl having 10 to 30 carbon atoms or alkylphenylhaving an alkyl group containing 4 to 30 carbon atoms. Still morepreferably, R₁ is alkylphenyl having an alkyl group containing 12 to 24carbon atoms.

R₂ is preferably alkylene having 2 to 4 carbon atoms. More preferably,R₂ is ethylene, i.e. --CH₂ CH₂ --.

Preferably, R₃, R₄, R₅, R₆, R₇ and R₈ are each independently hydrogen,methyl or ethyl. More preferably, R₃, R₄, R₅, R₆, R₇ and R₈ are eachindependently hydrogen or methyl. Most preferably, R₃, R₄, R₅, R₆, R₇and R₈ are hydrogen.

R₉ is preferably alkyl having 1 to 6 carbon atoms. More preferably, R₉is alkyl having 2 to 4 carbon atoms.

Preferably, m is 1. Preferably, n is an integer from 10 to 50. Morepreferably, n is an integer from 15 to 30.

A preferred group of poly(vinyl ether) amines are those of formula Iwherein A is derived from ammonia or a polyalkylene polyamine containing2 to about 12 nitrogen atoms and 2 to about 24 carbon atoms; R₁ is alkylhaving 8 to about 120 carbon atoms or alkylphenyl having an alkyl groupcontaining 4 to about 100 carbon atoms; R₂ is alkylene having 2 to 4carbon atoms; R₃, R₄, R₅, R₆, R₇ and R₈ are each independently hydrogen,methyl or ethyl; R₉ is alkyl having 1 to 6 carbon atoms; m is 0 or 1;and n is an integer from 10 to 50.

A more preferred group of poly(vinyl ether) amines are those of formulaI wherein A is derived from a polyalkylene polyamine having the formula:

    H.sub.2 N--(R.sub.10 NH).sub.y --H

wherein R₁₀ is alkylene having 2 to about 6 carbon atoms and y is aninteger from 1 to 3; R₁ is alkyl having 10 to 30 carbon atoms oralkylphenyl having an alkyl group containing 10 to 30 carbon atoms; R₂is ethylene; R₃, R₄, R₅, R₆, R₇ and R₈ are each hydrogen; R₉ is alkylhaving 2 to 4 carbon atoms; m is 0 or 1; and n is an integer from 10 to50.

A particularly preferred group of poly(vinyl ether) amines are thosehaving the formula: ##STR6## wherein R₁₁ is alkyl having 10 to 30 carbonatoms, R₁₂ is alkyl having 2 to 4 carbon atoms, p is an integer from 10to 50, q is an integer from 1 to 3, and W is a hydroxy(oxypropylene)group having the formula: ##STR7## or mixtures thereof.

The poly(vinyl ether) amines of the present invention will generallyhave a sufficient molecular weight so as to be non-volatile at normalengine intake valve operating temperatures. Typically, the molecularweight of the poly(vinyl ether) amines of this invention will range fromabout 600 to about 10,000, preferably from 1,000 to 3,000.

Definitions

As used herein the following terms have the following meanings unlessexpressly stated to the contrary.

The term "hydrocarbyl" refers to an organic radical primarily composedof carbon and hydrogen which may be aliphatic, alicyclic, aromatic orcombinations thereof (e.g. aralkyl or alkaryl). Such hydrocarbyl groupsare generally relatively free of aliphatic unsaturation, i.e. olefinicor acetylenic unsaturation, but may contain minor amounts ofheteroatoms, such as oxyqen or nitrogen, or halogens, such as chlorine.

The term "alkyl" refers to both straight- and branched-chain alkylgroups.

The term "lower alkyl" refers to alkyl groups having 1 to about 6 carbonatoms and includes primary, secondary and tertiary alkyl groups. Typicallower alkyl groups include, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl and the like.

The term "alkylene" refers to straight- and branched-chain alkylenegroups having at least 2 carbon atoms. Typical alkylene groups include,for example, ethylene (--CH₂ CH₂ --), propylene (--CH₂ CH₂ CH₂ --),isopropylene (--CH(CH₃)CH₂ --), n-butylene (-CH₂ CH₂ CH₂ CH₂ --).sec-butylene (--CH(CH₂ CH₃)CH₂ --) and the like.

The term "vinyl ether" refers to an α,β-unsaturated ether having thegeneral formula: ##STR8## wherein R_(a) and R_(b) are generally hydrogenor lower alkyl groups; and R_(c) is a hydrocarbyl group. The term "alkylvinyl ether" refers to a vinyl ether in which the hydrocarbyl group,R_(c), is an alkyl group.

The term "poly(vinyl ether)" refers to a vinyl ether polymer having thegeneral formula: ##STR9## wherein R_(a), R_(b) and R_(c) are as definedabove and z is an integer greater than 1. The term "vinyl ether unit"refers to one monomeric unit of a poly(vinyl ether) polymer. Whenreferring herein to the number of vinyl ether units in a particularpoly(vinyl ether) compound, it is to be understood that this numberrefers to the average number of vinyl ether units in such compoundsunless expressly stated to the contrary.

General Synthetic Procedures

The poly(vinyl ether) amines of this invention may be prepared by thefollowing general methods and procedures. It should be appreciated thatwhere typical or preferred process conditions (e.g. reactiontemperatures, times, mole ratios of reactants, solvents, pressures,etc.) are given, other process conditions may also be used unlessotherwise stated. Optimum reaction conditions may vary with theparticular reactants or solvents used, but such conditions can bedetermined by one skilled in the art by routine optimization procedures.

The poly(vinyl ether) amines of the present invention contain (a) apoly(vinyl ether) component, (b) an amine component, and (c) ahydroxy(oxypropylene) connecting group which covalently-links thepoly(vinyl ether) component and the amine component.

A. The Poly(Vinyl Ether) Component

The poly(vinyl ether) component of the poly(vinyl ether) amines of thepresent invention is a vinyl ether polymer containing about 6 to about100 vinyl ether units, including a hydrocarbyl vinyl ether unit andabout 5 to about 99 alkyl vinyl ether units. Generally, the poly(vinylether) component will have a hydrocarbyl vinyl ether unit at thebeginning of the vinyl ether polymer and will be terminated with abranched or unbranched ethylene group containing 2 to about 10 carbonatoms which is covalently-linked to the hydroxy(oxypropylene) connectinggroup.

The poly(vinyl ether) component of the poly(vinyl ether) amines of thisinvention is preferably prepared by polymerizing certain defined vinylether monomers under "living polymerization" conditions. The term"living polymerization" is well known in the art and refers topolymerization reactions which occur in the substantial absence of chaintransfer and termination reactions. Under such conditions, the reactiveend of the growing polymer is essentially stable indefinitely.Accordingly, each vinyl ether monomer can be added sequentially to thegrowing poly(vinyl ether) chain in a controlled step-by-step manner.Thus, living polymerization allows poly(vinyl ethers) to be preparedhaving a substantially predictable sequence of vinyl ether units.

In a preferred method of synthesizing the poly(vinyl ether) amines ofthe present invention, the living polymerization reaction is initiatedusing a hydrocarbyl vinyl ether monomer. Alkyl vinyl ether monomers arethen added sequentially in an amount sufficient to produce the desirednumber of vinyl ether units. The reaction is then quenched undersuitable aqueous conditions to form a carbonyl-terminated poly(vinylether) and the carbonyl group of the polymer is reduced to form ahydroxyl group. The resulting hydroxy-terminated poly(vinyl ether) isthen coupled to the amine component using an epihalohydrin to form thepoly(vinyl ether) amines of the present invention, as described infurther detail below.

The Hydrocarbyl Vinyl Ether Monomer

As indicated above, the poly(vinyl ether) amines of the presentinvention contain a hydrocarbyl ether moiety having a sufficient numberof carbon atoms to render the poly(vinyl ether) amine soluble inhydrocarbons boiling in the gasoline or diesel fuel range. Thissolubility condition is satisfied if the poly(vinyl ether) amine issoluble in hydrocarbon fuel at least to the extent of about 50 parts permillion by weight.

Typically, the hydrocarbyl ether moiety will contain at least about 5carbon atoms, preferably about 8 to about 120 carbon atoms, and morepreferably 10 to 36 carbon atoms.

The hydrocarbyl ether moiety of the poly(vinyl ether) amines of thisinvention is generally introduced into the poly(vinyl ether) componentby employing a hydrocarbyl vinyl ether monomer to initiate or begin theliving polymerization reaction. Suitable hydrocarbyl vinyl ethermonomers have the formula:

    R.sub.1 --(O--R.sub.2).sub.m --O--C(R.sub.4)═CHR.sub.3 (III)

wherein R₁ -R₄ and m are as defined above.

The hydrocarbyl vinyl ethers of formula III where m is 0 may beconveniently prepared from a monohydroxy compound and an olefin asrepresented by the reaction:

    R.sub.1 OH+R.sub.3 HC═CHR.sub.4 →R.sub.1 O--CR.sub.4 H═CR.sub.3 H                                          (1)

wherein R₁, R₃ and R₄ are as defined above. This reaction is catalyzedwith a Group VIII noble metal compound, such as platinum and palladiumchloride, and requires a regenerative oxidant capable of maintaining thenoble metal in oxidized form, such as cupric chloride. The reactionconditions are further described in U.S. Pat. Nos. 4,057,575 and4,161,610, both to D. L. Klass, the disclosures of which areincorporated herein by reference.

Alternatively, the hydrocarbyl vinyl ethers of formula III where m is 0can be prepared by a vinyl exchange reaction. Vinyl ethers and estersreadily exchange their vinyl groups with hydroxy compounds in presenceof a catalyst, such as palladium or mercury salts, according to thereaction:

    R.sub.1 OH+R.sub.13 O--CR.sub.4 H═CR.sub.3 H→R.sub.1 O--CR.sub.4 H═CR.sub.3 H+R.sub.13 OH                              (2)

wherein R₁, R₃ and R₄ are as defined above and R₁₃ is a lower alkylgroup, such as methyl, ethyl and the like, or an acyl group, such asacetate. Generally, an excess of the vinyl ether being used to donatethe vinyl group is employed in these reactions. Suitable conditions forvinyl exchange reactions are well known in the art. For example, thepalladium catalyzed reaction is described further in Japanese PatentApplication No. Sho 49-43909, published Apr. 25, 1974 by K. Takagi etal., and the mercury catalyzed reaction is described by M. F.Shostakovshii et al. in Russian Chemical Reviews, 37, 907 (1968) andreferences cited therein.

Especially preferred hydrocarbyl vinyl ether monomers for use in thepresent invention are those of formula III where m is 1. These monomerscan be conveniently prepared by reacting a monohydroxy compound, R₁ OHor a suitable salt thereof, with a haloalkyl vinyl ether having theformula:

    Y--R.sub.2 --O--C(R.sub.3)═CHR.sub.4                   (IV)

wherein R₂, R₃ and R₄ are as defined above and Y is a halogen, such aschloride, bromide or iodide. Preferably, R₃ and R₄ are hydrogen and R₂is an alkylene group containing 2 to 4 carbon atoms. Most preferably, R₂is ethylene (--CH₂ CH₂ --) and Y is chloride.

Exemplary haloalkyl vinyl ethers include 2-chloroethyl vinyl ether,2-chloroethyl propenyl ether, 3-bromo-n-propyl vinyl ether, and4-chloro-n-butyl vinyl ether and the like. Some of these haloalkyl vinylethers are commercially available, such as 2-chloroethyl vinyl ether,which may be purchased from Aldrich Chemical Company, Inc., Milwaukee,Wis. 53233. Others can be readily prepared by the procedures describedby M. F. Shostakovshii et al. in Russian Chemical Reviews, 37, 913-914(1968) and references cited therein.

The reaction of a monohydroxy compound, R₁ OH or a suitable saltthereof, with a haloalkyl vinyl ether of formula IV is typicallyconducted by contacting the monohydroxy reactant with about 1.0 to about2.0 molar equivalents of the haloalkyl vinyl ether in an inert solvent,such as dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and the like,at a temperature ranging from about 30° C. to about 120° C. for about 1to about 24 hours. Under these conditions, the monohydroxy compound, R₁OH, substantially displaces the halogen forming the desired hydrocarbylvinyl ether monomers of Formula III wherein m is 1. Preferably, a saltof the monohydroxy compound, such as the sodium, potassium or magnesiumsalt, is prepared prior to reaction with the haloalkyl vinyl ether byprocedures which are well known in the art. For example, the salt of amonohydroxy alcohol can be prepared by contacting the alcohol withsodium or potassium metal, or sodium or potassium hydride in an inertsolvent. Alternatively, the salt of an alkylphenol can preferably beprepared by contacting the phenol with sodium or potassium hydroxide inan inert solvent.

The monohydroxy compound R₁ OH, used in the above reactions, ispreferably a straight- or branched-chain aliphatic alcohol having 8 toabout 120 carbon atoms, more preferably 10 to 30 carbon atoms; or analkylphenol having an alkyl substituent containing about 4 to about 100carbon atoms, more preferably 10 to 30 carbon atoms, still morepreferably 12 to 24 carbon atoms.

Preferred straight-chain alcohols have about 8 to about 30 carbon atomsand include, for example, octanol, nonanol, decanol, hexadecanol (cetylalcohol), octadecanol (stearyl alcohol) and the like. Particularlypreferred straight-chain alcohols are those derived from linear C₁₀ toC₃₀ alpha olefins and mixtures thereof.

Preferred branched-chain alcohols include those derived from polymers ofC₂ to C₆ olefins, such as alcohols derived from polypropylene andpolybutene. Particularly preferred are polypropylene alcohols having 9to about 60 carbon atoms and polybutene alcohols having 8 to about 120carbon atoms. Alcohols derived from the alpha olefin oligomers of C₈ toC₁₆ alpha olefins, such as the dimer, trimer and tetramer of decene asdescribed in U.S. Pat. No. 4,045,508, issued Aug. 30, 1977 to B. L.Cupples et al., are also useful in this invention.

Many of these straight- and branched-chain alcohols are commerciallyavailable and the others can be readily prepared from the correspondingolefins by conventional procedures. Suitable procedures for preparingalcohols from olefins are described for example in I. T. Harrison and S.Harrison, Compendium of Organic Synthetic Methods, pp. 119-122,Wiley-Interscience, New York (1971) and references cited therein.

In an especially preferred embodiment of the present invention, themonohydroxy compound, R₁ OH, used to prepare the hydrocarbyl vinyl ethermonomers of formula III, is an alkylphenol having the formula: ##STR10##wherein R₁₄ is a straight- or branched-chain alkyl group having about 4to about 100 carbon atoms, preferably 10 to 30 carbon atoms, morepreferably 12 to 24 carbon atoms; and v is 1 or 2, preferably 1.

When v is one, the alkylphenol of formula V is a monoalkylphenol andwhen v is two, the alkylphenol is a dialkylphenol. Both mono- anddialkylphenols or mixtures thereof are suitable for use in the presentinvention, although monoalkylphenols are preferred. Most preferably, thealkylphenol of formula V is a monoalkylphenol having the alkyl group inthe para position.

Numerous methods are known in the art for preparing the alkylphenols offormula V and any of these methods are suitable for use in the presentinvention. Generally, the alkylphenols of formula V are prepared byreacting an olefin or olefin mixture with phenol in the presence of analkylation catalyst. Suitable alkylation catalysts include sulfonic acidcatalysts, such as Amberlyst® 15, and Lewis acid catalysts, such asboron trifluoride etherate. The alkylation reaction is typicallyconducted at a temperature from about 25° C. to about 125° C. Thereaction may be conducted in an essentially inert solvent or in theabsence of a solvent. Examples of inert solvents include chlorobenzeneand hexane.

Monoalkylphenols may be preferentially prepared by employing an excessof phenol in the alkylation reaction, typically 2 to 2.5 equivalents ofphenol for each equivalent of olefin. The excess phenol is preferablyrecovered and recycled. Dialkylphenols may be preferentially prepared byemploying a molar excess of olefin in the alkylation reaction, such astwo or more equivalents of olefin per equivalent of phenol.

Preferred monoalkylphenols for use in the present invention include, forexample, decylphenol, undecylphenol, dodecylphenol, tetradecylphenol,pentadecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol,hexacosylphenol, triacontylphenol and the like. Also, mixtures ofalkylphenols may be employed, such as a mixture of C₁₄ -C₁₈alkylphenols, a mixture of C₁₈ -₂₄ alkylphenols, a mixture of C₂₀ -C₂₄alkylphenols, or a mixture of C₁₆ -C₂₆ alkylphenols.

Particularly preferred alkylphenols are those derived from alkylation ofphenol with polymers or oligomers of C₃ to C₆ olefins, such aspolypropylene or polybutene. These polymers typically contain about 9 toabout 100 carbon atoms, preferably about 10 to about 30 carbon atoms. Anespecially preferred alkylphenol is prepared by alkylating phenol with apropylene polymer having an average of 4 units. This polymer has thecommon name of propylene tetramer and is commercially available.

Alkylphenols derived from alpha olefin oligomers of C₈ to C₁₆ alphaolefins, such as the dimer, trimer and tetramer of decene, are alsouseful in this invention. Such alkylphenols are described in PCTInternational patent application Publication No. WO 90/07564, publishedJul. 12, 1990, the disclosure of which is incorporated herein byreference.

The Alkyl Vinyl Ether Monomers

As described above, the first vinyl ether unit of the poly(vinyl ether)component is typically derived from a hydrocarbyl vinyl ether monomer.The subsequent units of the polymer are preferably derived from alkylvinyl ether monomers having the formula:

    R.sub.5 HC═CR.sub.6 --OR.sub.9                         (VI)

wherein R₅, R₆ and R₉ are as defined above. Preferably, R₅ and R₆ areeach independently hydrogen or methyl. More preferably, R₅ and R₆ areboth hydrogen.

The alkyl group R₉ can be a straight- or branched-chain alkyl group andpreferably contains 1 to 6 carbon atoms, more preferably 2 to 4 carbonatoms. Particularly preferred alkyl groups are methyl, ethyl, n-propyl,isopropyl, n-butyl and isobutyl groups. Especially preferred alkylgroups are ethyl and isobutyl groups.

Suitable alkyl vinyl ethers include methyl vinyl ether (H₂C═CH--O--CH₃), ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinylether, n-butyl vinyl ether, isobutyl vinyl ether and the like.

A number of suitable alkyl vinyl ether monomers are commerciallyavailable. Others can be readily prepared by the procedures discussedabove for hydrocarbyl vinyl ether monomers. Alternatively, alkyl vinylether monomers can be produced on a commercial scale from alcohols andacetylene as described in Kirk-Othmer, Encyclopedia of ChemicalTechnology, 3rd Ed., Vol. 1, p. 269, Wiley-Interscience, New York(1983).

Polymerization Conditions

The poly(vinyl ether) component of the poly(vinyl ether) amines of thisinvention is preferably prepared by the living polymerization of ahydrocarbyl vinyl ether monomer and alkyl vinyl ether monomers. Livingpolymerization of vinyl ethers is well known in the art and is furtherdescribed, for example, by T. Higashimura et al. in ComprehensivePolymer Science, Pergamon, Oxford, 1989, Vol. 3, Part I, Chapter 42 andreferences cited therein. Living polymerization reactions employingvinyl ether monomers are typically conducted using an "initiatingsystem" which comprises hydrogen iodide (HI) and a weak Lewis acid, suchas zinc iodide (ZnI₂) or iodine (I₂). In the present invention, ahydrogen iodide/zinc iodide initiating system is particularly preferred.Other initiating systems may also be employed, such as a mixture of ahalogenated aliphatic acid and a zinc salt of a halogenated aliphaticacid as described in U.S. Pat. No. 5,026,799, or the initiating systemsdescribed by M. Sawamoto et al. in Makromol. Chem., Macromol. Symp.,1990, 32, 131 and references cited therein.

Generally, the living polymerization reaction will be conducted in asubstantially anhydrous inert solvent at a temperature of about -78° C.to about 50° C., preferably -20° C. to 25° C. Suitable inert solventsinclude benzene, toluene, dichloromethane, diethyl ether and the like.Preferably, the polymerization reaction will be conducted under a dryinert gas atmosphere, such as nitrogen or argon, at about atmospheric orambient pressure.

Typically, in the first step of the living polymerization reaction, ahydrocarbyl vinyl ether monomer of formula III is contacted with about1.0 molar equivalents of hydrogen iodide to form an adduct according tothe reaction: ##STR11##

wherein R₁ -R₄ and m are as defined above. Preferably, the hydrogeniodide is added as a solution in an inert solvent, such as hexane. Thisreaction is generally conducted for about 1.0 to about 20 minutes whichis usually sufficient to result in the substantially complete conversionof the hydrocarbyl vinyl ether monomer to the adduct VII.

In the second step of the living polymerization reaction, an alkyl vinylether monomer of formula VI or a mixture of such alkyl vinyl ethermonomers is added to the solution containing the adduct VII, andsubsequently, zinc iodide is introduced to initiate the polymerizationreaction. Typically, a molar ratio of hydrogen iodide to zinc iodideranging from about 5:1 to about 500:1, preferably about 50:1, will beemployed.

Generally, the molar ratio of alkyl vinyl ether monomer to adduct VIIwill range from about 6:1 to about 100:1, preferably 11:1 to 51:1, morepreferably 16:1 to 31:1. The alkyl vinyl ether monomer or mixture ofmonomers may be added entirely at the beginning of the polymerizationreaction or may be added sequentially during the course of the reaction.By adding a mixture of alkyl vinyl ether monomers at the beginning ofthe reaction, a poly(vinyl ether) having an essentially randomdistribution of alkyl vinyl ether units can be produced. Alternatively,the sequential addition of different alkyl vinyl ether monomers producesa poly(vinyl ether) having substantial blocks of identical alkyl vinylether units.

The time employed for the polymerization reaction can vary over a widerange and will depend to some extent on the reaction temperature and onthe vinyl ether monomers used in the polymerization process. Generally,the reaction will be conducted for about 0.25 to about 20 hours,preferably 10 to 2.0 hours or until essentially all the alkyl vinylether monomers have reacted to form polymer. Completion of thepolymerization reaction can be monitored by observing the disappearanceof the vinylic proton(s) from the alkyl vinyl ether monomers by ¹ H NMR,if desired. When essentially all of the alkyl vinyl ether monomer hasreacted to form polymer, the reactive terminal end of the polymer isquenched by contacting the reaction mixture with about 5 to about 20equivalents of an aqueous alkali metal carbonate solution, such asaqueous potassium or sodium carbonate. This affords acarbonyl-terminated poly(vinyl ether) having the formula: ##STR12##wherein R₁ -R₉, m and n are as defined above. The quenching reaction istypically conducted at about -20° C. to about 25° C. for about 0.1 toabout 2 hours.

In a preferred method of preparing the poly(vinyl ether) amines of thepresent invention, the carbonyl group of the poly(vinyl ether) offormula VIII is reduced with a suitable reducing agent, such as a metalhydride reagent, to form a hydroxy-terminated poly(vinyl ether) havingthe formula: ##STR13## wherein R₁ -R₉, m and n are as defined above. Aparticularly preferred reducing agent is sodium borohydride.

Typically, the reduction reaction is effected by contacting thecarbonyl-terminated poly(vinyl ether) of formula VIII with about 2 toabout 10 molar equivalents of sodium borohydride in an essentially inertsolvent. Suitable solvents include methanol, ethanol, propanol and thelike. Ethanol is a particularly preferred solvent. The reaction isusually conducted at about 0° C. to about 40° C. for about 2 to about 24hours. Other suitable methods for reducing carbonyl compounds toalcohols can be found, for example, in I. T. Harrison and S. Harrison,Compendium of Organic Synthetic Methods, pp. 81-84 and 111-118,Wiley-Interscience, New York (1971) and references cited therein.

The hydroxy-terminated poly(vinyl ether) of formula IX may then becoupled with a suitable amine component using an epihalohydrin asdescribed in further detail below.

B. The Amine Component

As indicated above, the poly(vinyl ether) amines of the presentinvention contain an amine component which is covalently linked to theaforementioned poly(vinyl ether) component through ahydroxy(oxypropylene) connecting group.

In general, the amine component will contain an average of at leastabout one basic nitrogen atom per molecule. A "basic nitrogen atom" isone that is titratable by a strong acid, for example, a primary,secondary or tertiary amine nitrogen Preferably, at least one of thebasic nitrogen atoms of the amine component will be primary or secondaryamine nitrogen, more preferably at least one will be a primary aminenitrogen.

The amine component of the poly(vinyl ether) amines of this invention ispreferably derived from ammonia (NH₃), a monoamine having 1 to about 8carbon atoms, or a polyamine containing 2 to about 12 amine nitrogenatoms and from 2 to about 40 carbon atoms. Amine components derived fromammonia or a polyamine are particularly preferred, especially thosederived from polyamines having a carbon-to-nitrogen ratio of from about1:1 to 10:1.

In preparing the compounds of this invention using a polyamine where thevarious nitrogen atoms of the polyamine are not geometricallyequivalent, several substitutional isomers are possible and each ofthese possible isomers is encompassed within this invention.

Suitable polyamines can have a straight- or branched-chain structure andmay be cyclic or acyclic or combinations thereof. Generally, the aminenitrogen atoms of such polyamines will be separated from one another byat least two carbon atoms, i.e. polyamines having an aminal structureare not suitable. The polyamine may also contain one or more oxygenatoms, typically present as an ether or a hydroxyl group.

A particularly preferred group of polyamines for use in the presentinvention are polyalkylene polyamines, including alkylene diamines. Suchpolyalkylene polyamines will typically contain 2 to about 12 nitrogenatoms and 2 to about 24 carbon atoms. Preferably, the alkylene groups ofsuch polyalkylene polyamines will contain from 2 to about 6 carbonatoms, more preferably from 2 to 4 carbon atoms.

Examples of suitable polyalkylene polyamines include ethylenediamine,propylenediamine, isopropylenediamine, butylenediamine,pentylenediamine, hexylenediamine, diethylenetriamine,dipropylenetriamine, diisopropylenetriamine, dibutylenetriamine,di-secbutylenetriamine, triethylenetetraamine, tripropylenetetraamine,triisobutylenetetraamine, tetraethylenepentamine, pentaethylenehexamineand mixtures thereof.

Particularly suitable polyalkylene polyamines are those having theformula:

    H.sub.2 N--(R.sub.10 NH).sub.y --H                         (X)

wherein R₁₀ is a straight- or branched-chain alkylene group having 2 toabout 6 carbon atoms, preferably 2 to 4 carbon atoms, most preferably 2carbon atoms, i.e. ethylene (--CH₂ CH₂ --); and y is an integer from 1to 3, preferably 1 or 2.

Particularly preferred polyalkylene polyamines are ethylenediamine,diethylenetriamine and triethylenetetraamine. Most preferred isethylenediamine.

Also contemplated for use in the present invention are cyclic polyamineshaving one or more 5- to 6-membered rings. Such cyclic polyaminescompounds include piperazine, 2-methylpiperazine,N-(2-aminoethyl)piperazine, N-(2-hydroxyethyl)piperazine,1,2-bis-(N-piperazinyl)ethane, 3-aminopyrrolidine,N-(2-aminoethyl)pyrrolidine and the like. Among the cyclic polyamines,the piperazines are preferred.

Alternatively, the amine component may be derived from ammonia or amonoamine having 1 to about 8 carbon atoms. Suitable monoamines includeprimary N-alkylamines and secondary N,N-dialkylamines. Among themonoamines, primary N-alkylamines having an unbranched alkyl groupcontaining 1 to about 4 carbon atoms are preferred, such as methylamine,ethylamine, n-propylamine, and n-butylamine. Most preferred among themonoamines is methylamine.

Many of the amines suitable for use in present invention arecommercially available and others many be prepared by methods which arewell known in the art. For example, methods for preparing amines andtheir reactions are detailed in Sidgewick's "The Organic Chemistry ofNitrogen", Clarendon Press, Oxford, 1966; Noller's "Chemistry of OrganicCompounds", Saunders, Philadelphia, 2nd Ed., 1957; and Kirk-Othmer's"Encyclopedia of Chemical Technology", 2nd Ed., especially Volume 2, pp.99-116.

C. The Hydroxy (oxypropylene) Connecting Group

The hydroxy(oxypropylene) connecting group which covalently links thepoly(vinyl ether) component to the amine component will generally bederived from an epihalohydrin and has the formula: ##STR14## mixturesthereof, wherein the ether oxygen may be regarded as being derived fromthe hydroxyl group of a hydroxy-terminated poly(vinyl ether) of formulaIX. It is believed that the reaction conditions used to prepared thepoly(vinyl ether) amines of the present invention favor the formation ofthe --O--CH₂ CHOHCH₂ -- group and that this group predominates.

The poly(vinyl ether) amines of the present invention are generallyprepared by contacting a hydroxy-terminated poly(vinyl ether) of formulaIX with an epihalohydrin to produce a poly(vinyl ether) epoxide orhalohydrin intermediate. This intermediate is then contacted with asuitable amine to afford a poly(vinyl ether) amine having ahydroxy(oxypropylene) connecting group.

Suitable epihalohydrins have the formula: ##STR15## wherein X ishalogen, preferably chlorine or bromine. Epichlorohydrin andepibromohydrin are commercially available reagents. Alternatively, theymay be prepared by the procedures described in Organic Synthesis,Collective Volume II, pp. 256-258, John Wiley & Sons, New York (1943).

The reaction of the hydroxy-terminated poly(vinyl ether) of formula IXwith an epihalohydrin is typically conducted on an essentially equimolarbasis. The reaction may be conducted by first forming a suitable salt ofhydroxyl group of the hydroxy-terminated poly(vinyl ether), such as thesodium or potassium salt, in an inert solvent using conventionalprocedures, such as by contacting IX with sodium hydride. This alkoxideintermediate may then be reacted with an epihalohydrin by adding theepihalohydrin to the solution or mixture containing the alkoxideintermediate. Epibromohydrin is particularly preferred in this reaction.The reaction is generally conducted at a temperature ranging from about0° C. to about 150° C. for about 1 to about 24 hours, and typicallyaffords a poly(vinyl ether) epoxide intermediate.

Alternatively, the hydroxy-terminated poly(vinyl ether) may be reactedwith an epihalohydrin by contacting the hydroxy-terminated poly(vinylether) of formula IX with the epihalohydrin in the presence of acatalyst. Generally, this reaction is performed at a temperature rangingfrom about 30° C. to about 100° C., preferably from about 50° C. toabout 80° C. The reaction is typically complete within about 0.5 toabout 5 hours, and typically affords a poly(vinyl ether) halohydrinintermediate.

Suitable catalysts for the reaction include Friedel-Crafts typecatalysts, such as AlCl₃, BF₃, ZnCl₂, FeCl₃ and the like; and acidcatalysts, such as HF, H₂ SO₄, H₃ PO₄ and the like. A preferred catalystis boron trifluoride which is conveniently employed as an etherate.Generally, about 0.1 to about 5 parts catalyst per 100 parts by weighthydroxy-terminated poly(vinyl ether) are used.

A poly(vinyl ether) amine of the present invention is then formed bycontacting the epoxide or halohydrin intermediate with a suitable aminecomponent at a temperature ranging from about 30° C. to about 150° C.for about 1 to about 24 hours. This reaction may be conducted with orwithout an inert solvent. Suitable solvents include benzene, toluene,xylene and the like. The molar ratio of amine to epoxide or halohydrinintermediate will generally range from about 2:1 to about 20:1,preferably 5:1 to 10:1. The reaction will typically be conducted atatmospheric pressure, however, when employing a lower-boiling aminecomponent, such as ammonia, higher pressures may be preferred. Thedesired product may be obtained by washing the reaction mixture withwater and stripping the mixture, usually under vacuum, to remove anyresidual solvent.

Fuel Compositions

The poly(vinyl ether) amines of the present invention are useful asadditives in hydrocarbon fuels to prevent and control engine deposits,particularly intake valve deposits. Typically, the desired depositcontrol will be achieved by operating an internal combustion engine witha fuel composition containing a poly(vinyl ether) amine of the presentinvention. The proper concentration of additive necessary to achieve thedesired deposit control varies depending upon the type of fuel employed,the type of engine, and the presence of other fuel additives.

In general, the concentration of the poly(vinyl ether) amines of thisinvention in hydrocarbon fuel will range from about 50 to about 2500parts per million (ppm) by weight, preferably from 75 to 1,000 ppm. Whenother deposit control additives are present, a lesser amount of thepresent additive may be used. Furthermore, lower concentrations of, forexample, 30 to 70 ppm may be preferred when the present additives areemployed as carburetor detergents only.

The poly(vinyl ether) amines of the present invention may be formulatedas a concentrate using an inert stable oleophilic (i.e., dissolves ingasoline) organic solvent boiling in the range of about 150° F. to 400°F. (about 65° C. to 205° C.). Preferably, an aliphatic or an aromatichydrocarbon solvent is used, such as benzene, toluene, xylene orhigher-boiling aromatics or aromatic thinners. Aliphatic alcoholscontaining about 3 to 8 carbon atoms, such as isopropanol,isobutylcarbinol, n-butanol and the like, in combination withhydrocarbon solvents are also suitable for use with the presentadditives. In the concentrate, the amount of the additive will begenerally range from about 10 to about 70 weight percent, preferably 10to 50 weight percent, more preferably from 10 to 25 weight percent.

In gasoline fuels, other fuel additives may be employed with theadditives of the present invention, including, for example, oxygenates,such as t-butyl methyl ether, antiknock agents, such asmethylcyclopentadienyl manganese tricarbonyl, and otherdispersants/detergents, such as hydrocarbyl amines,hydrocarbyl(polyoxyalkylene) amines, or succinimides. Additionally,antioxidants, metal deactivators and demulsifiers may be present.

In diesel fuels, other well-known additives can be employed, such aspour point depressants, flow improvers, cetane improvers, and the like.

A fuel-soluble, nonvolatile carrier fluid or oil may also be used withthe poly(vinyl ether) amines of this invention. The carrier fluid is achemically inert hydrocarbon-soluble liquid vehicle which substantiallyincreases the nonvolatile residue (NVR), or solvent-free liquid fractionof the fuel additive composition while not overwhelmingly contributingto octane requirement increase. The carrier fluid may be a natural orsynthetic oil, such as mineral oil, refined petroleum oils, syntheticpolyalkanes and alkenes, including hydrogenated and unhydrogenatedpolyalphaolefins, and synthetic polyoxyalkylene-derived oils, such asthose described, for example, in U.S. Pat. No. 4,191,537 to Lewis.

These carrier fluids are believed to act as a carrier for the fueladditives of the present invention and to assist in removing andretarding deposits. The carrier fluid may also exhibit synergisticdeposit control properties when used in combination with the poly(vinylether) amines of this invention.

The carrier fluids are typically employed in amounts ranging from about100 to about 5000 ppm by weight of the hydrocarbon fuel, preferably from400 to 3000 ppm of the fuel. Preferably, the ratio of carrier fluid todeposit control additive will range from about 0.5:1 to about 10:1, morepreferably from 2:1 to 5:1, most preferably about 4:1.

When employed in a fuel concentrate, carrier fluids will generally bepresent in amounts ranging from about 20 to about 60 weight percent,preferably from 30 to 50 weight percent.

EXAMPLES

The following examples are presented to illustrate specific embodimentsof the present invention and synthetic preparations thereof and shouldnot be interpreted as limitations upon the scope of the invention.

EXAMPLE 1 Preparation of 2-(p-Dodecylphenoxy)ethyl Vinyl Ether ##STR16##

To a flask equipped with a mechanical stirrer, reflux condenser,addition funnel, thermometer and nitrogen inlet was added 104.96 gramsof p-dodecylphenol (prepared by alkylating phenol with propylenetetramer), 120 mL of anhydrous dimethylsulfoxide and 24 grams of sodiumhydroxide. The mixture was stirred at room temperature for 30 minutesand then heated to 70°-75° C. with a heating mantle for 2 hours. Theheating mantle was removed and 64 grams of 2-chloroethyl vinyl etherwere added dropwise at a rate to maintain the temperature below 80° C.After the addition was complete, the reaction was heated to 75° C. for16 hours, cooled to room temperature and poured into 500 mL of water.The water was extracted three times with diethyl ether and the combinedorganic layers were washed three times with water and once withsaturated aqueous sodium chloride solution. The organic layer was thendried over anhydrous sodium sulfate, filtered and the solvents removedin vacuo to yield 132.2 grams of the desired ether as an orange oil.

EXAMPLE 2 Preparation ofα-(Formylmethyl)-ω-[1-(2'-(p-dodecylohenoxy)ethoxy)ethyl]poly(1-ethoxyethylene)##STR17##

To an oven-dried flask equipped with a thermometer, magnetic stirrer,septa, addition funnel and nitrogen inlet was added 18.75 grams of2-(p-dodecylphenoxy)ethyl vinyl ether from Example 1 and 1.5 L ofanhydrous toluene. The contents of the flask were cooled to -10° C. and109.5 mL of anhydrous 0.515N hydrogen iodide in hexane were added at arate to maintain the temperature below -10° C. The reaction was stirredat -10° C. for 10 minutes and 102.4 mL of ethyl vinyl ether (previouslydistilled from calcium hydride and then distilled from sodium) wereadded followed by 0.36 grams of anhydrous zinc iodide dissolved in 5.7mL of anhydrous diethyl ether. The zinc iodide solution was added at arate to maintain the temperature at -10° C. The reaction mixture wasstirred at -10° C. for 1.5 hours, then quenched with an aqueous solutionof potassium carbonate (77.97 grams dissolved in 312 mL of water) andstirred for 15 minutes. A 10% aqueous sodium thiosulfate solution (500mL) was added and the cooling bath was removed. The organic layer wasseparated and washed twice with 10% aqueous sodium thiosulfate, threetimes with water and once with saturated aqueous sodium chloride. Theorganic layer was then dried over anhydrous sodium sulfate, filtered andthe solvents removed in vacuo to yield 98.54 grams of the desiredaldehyde.

EXAMPLE 3 Preparation ofα-(2-Hydroxyethyl)-ω-[1-(2'-(p-dodecylphenoxy)ethoxy)ethyl]poly(1-ethoxyethylene)##STR18##

Sodium borohydride (11.78 grams) was added to a solution of 105.0 gramsof the aldehyde from Example 2 dissolved in 530 mL of ethanol undernitrogen. The reaction was stirred at room temperature for 16 hours and160 mL of 10% aqueous sodium hydroxide were added. Most of the solventwas removed in vacuo and 650 mL of 10% aqueous sodium hydroxide wereadded. The aqueous layer was extracted four times with hexane. Thecombined organic layers were washed once with saturated aqueous sodiumchloride, dried over anhydrous sodium sulfate, filtered and the solventsremoved in vacuo to yield 91.03 grams of an oil. The oil waschromatographed on silica gel, eluting first with hexane/diethyl ether(6:4) and then with diethyl ether/hexane/methanol (8:1.8:0.2) to yield81.20 grams of the desired alcohol.

EXAMPLE 4 Preparation ofα-(2-Gycidyloxyethyl)-ω-[1-(2'-(p-dodecylphenoxy)ethoxy)ethyl]poly(1-ethoxyethylene)##STR19##

To a flask equipped with a magnetic stirrer, reflux condenser, septa andnitrogen inlet was added 0.0855 grams of a 35 wt % dispersion ofpotassium hydride in mineral oil and 25 mL of anhydrous tetrahydrofuran.The alcohol (3.0 grams) from Example 3 dissolved in 25 mL of anhydroustetrahydrofuran was added dropwise and the reaction was stirred for 45minutes at room temperature. Epichlorohydrin (0.21 mL) was added and thereaction was stirred at room temperature for 1.5 hours followed byrefluxing for 16 hours. The reaction was cooled to room temperature,quenched with 5 mL of methanol and diluted with 150 mL of diethyl ether.The resulting mixture was washed twice with saturated aqueous sodiumchloride, dried over anhydrous magnesium sulfate, filtered and thesolvent removed in vacuo to give an oil. The oil was chromatographed onsilica gel, eluting with diethyl ether/hexane/methanol (7:2.8:0.2) toyield 1.4 grams of the desired epoxide.

EXAMPLE 5 Preparation ofα-[2-(3'-N-(2"-Aminoethyl)amino)-2'-hydroxypropyl)ethyl)-ω-[1-((2p'-dodecylphenoxy)ethoxy)ethyl]poly(1-ethoxyethylene) ##STR20##

The epoxide (1.4 grams) from Example 4 and 10 mL of diethylenetriaminewere heated at 150° C. for 16 hours. The reaction was diluted with 100mL of dichloromethane and washed three times with water and then oncewith saturated aqueous sodium chloride. The organic layer was dried overanhydrous sodium sulfate, filtered and the solvent removed in vacuo togive an oil. The oil was chromotographed on silica gel, eluting firstwith dichloromethane/isopropanol/ammonium hydroxide (9:0.9:0.1) followedby hexane/ diethyl ether/methanol/isopropylamine (4:4:1.5:0.5) to yield0.12 grams of the desired product. The product had an average of 22ethoxyethylene units. ¹ H NMR (CDCl₃) δ7.05-7.25 (m, 2H), 6.7-6.9 (m,2H), 4.05-4.15 (t, 2H), 2.8-4.0 (m, 74H), 2.6-2.8 (m, 10H), 0.6-2.0 (m,140H).

WHAT IS CLAIMED IS:
 1. A compound of the formula: ##STR21## wherein A isan amine moiety having at least one basic nitrogen atom; R₁ is ahydrocarbyl group having a sufficient number of carbon atoms to rendersaid compound soluble in hydrocarbons boiling in the gasoline or dieselfuel range;R₂ is alkylene having 2 to about 8 carbon atoms; R₃, R₄, R₅,R₆, R₇ and R₈ are each independently hydrogen or lower alkyl having 1 toabout 4 carbon atoms; R₉ is alkyl having 1 to about 10 carbon atoms; mis 0 or 1; n is an integer from 5 to 99; and W is ahydroxy(oxypropylene) group having the formula: ##STR22## or mixturesthereof.
 2. The compound according to claim 1 wherein n is an integerfrom 10 to
 50. 3. The compound according to claim 2 wherein n is aninteger from 15 to
 30. 4. The compound according to claim 2 wherein saidamine moiety is derived from ammonia, a monoamine having 1 to about 8carbon atoms, or a polyamine containing 2 to about 12 amine nitrogenatoms and from 2 to about 40 carbon atoms.
 5. The compound according toclaim 4 wherein R₁ is alkyl having 8 to about 120 carbon atoms oralkylphenyl having an alkyl group containing 4 to about 100 carbonatoms.
 6. The compound according to claim 5 wherein R₂ is alkylenehaving 2 to 4 carbon atoms; R₃, R₄, R₅, R₆, R₇ and R₈ are eachindependently hydrogen, methyl, or ethyl; and R₉ is alkyl having 1 to 6carbon atoms.
 7. The compound according to claim 6 wherein said aminemoiety is derived from a polyalkylene polyamine containing 2 to about 12nitrogen atoms and 2 to about 24 carbon atoms.
 8. The compound accordingto claim 7 wherein R₁ is alkyl having 10 to 30 carbon atoms oralkylphenyl having an alkyl group containing 10 to 30 carbon atoms. 9.The compound according to claim 8 wherein R₂ is ethylene; R₃, R₄, R₅,R₆, R₇ and R₈ are each hydrogen; and R₉ is alkyl having 2 to 4 carbonatoms.
 10. The compound according to claim 9 wherein said polyalkylenepolyamine has the formula:

    H.sub.2 N-(R.sub.10 NH).sub.y -H

wherein R₁₀ is alkylene having 2 to about 6 carbon atoms and y is aninteger from 1 to
 3. 11. The compound according to claim 8 wherein R₁₀ cis ethylene.
 12. The compound according to claim 11 wherein y is 1 or 2.13. The compound according to claim 11 wherein R₁ is alkylphenyl havingan alkyl group containing 12 to 24 carbon atoms.
 14. The compoundaccording to claim 13 wherein said alkyl group is derived from propylenetetramer.
 15. The compound according to claim 14 wherein R₉ is ethyl orisobutyl.
 16. The compound according to claim 15 wherein m is
 1. 17. Afuel composition comprising a major amount of hydrocarbons boiling inthe gasoline or diesel range and an effective detergent amount of acompound of the formula: ##STR23## wherein A is an amine moiety havingat least one basic nitrogen atom; R₁ is a hydrocarbyl group having asufficient number of carbon atoms to render said compound soluble inhydrocarbons boiling in the gasoline or diesel fuel range;R₂ is analkylene group having 2 to about 8 carbon atoms; R₃, R₄, R₅, R₆, R₇ andR₈ are each independently hydrogen or a lower alkyl group having 1 toabout 4 carbon atoms; R₉ is a straight- or branched-chain alkyl grouphaving 1 to about 10 carbon atoms; m is 0 or 1; n is an integer from 5to 99; and W is a hydroxy(oxypropylene) group having the formula:##STR24## or mixtures thereof.
 18. The fuel composition according toclaim 17 wherein said amine moiety is derived from ammonia, a monaminehaving 1 to about 8 carbon atoms, or a polyamine containing 2 to about12 amine nitrogen atoms and from 2 to about 40 carbon atoms; R₁ is alkylhaving 8 to about 120 carbon atoms or alkylphenyl having an alkyl groupcontaining 4 to about 100 carbon atoms; and n is an integer from 10 to50.
 19. The fuel composition according to claim 18 wherein R₂ isalkylene having 2 to 4 carbon atoms; R₃, R₄, R₅, R₆, R₇ and R₈ are eachindependently hydrogen, methyl, or ethyl; and R₉ is alkyl having 1 to 6carbon atoms.
 20. The fuel composition according to claim 19 whereinsaid amine moiety is derived from a polyalkylene polyamine containing 2to about 12 nitrogen atoms and 2 to about 24 carbon atoms; and R₁ isalkyl having 10 to 30 carbon atoms or alkylphenyl having an alkyl groupcontaining 10 to 30 carbon atoms.
 21. The fuel composition according toclaim 20 wherein R₂ is ethylene; R₃, R₄, R₅, R₆, R₇ and R₈ are eachhydrogen; and R₉ is alkyl having 2 to 4 carbon atoms.
 22. The fuelcomposition according to claim 21 wherein said polyalkylene polyaminehas the formula:

    H.sub.2 N-(R.sub.10 NH).sub.y -H

wherein R₁₀ is alkylene having 2 to about 6 carbon atoms and y is aninteger from 1 to
 3. 23. The fuel composition according to claim 22wherein R₁₀ is ethylene.
 24. The fuel composition according to claim 23wherein y is 1 or
 2. 25. The fuel composition according to claim 17wherein said composition contains about 50 to about 2500 parts permillion by weight of said compound.
 26. The fuel composition accordingto claim 25 wherein said composition contains about 100 to about 5000parts per million by weight of a fuel-soluble, nonvolatile carrierfluid.
 27. A method for reducing engine deposits in an internalcombustion engine comprising operating said engine with the fuelcomposition of claim
 17. 28. A fuel concentrate comprising an inertstable oleophilic organic solvent boiling in the range of from about150° F. to 400° F. and from about 10 to about 70 weight percent of acompound of the formula: ##STR25## wherein A is an amine moiety havingat least one basic nitrogen atom; R₁ is a hydrocarbyl group having asufficient number of carbon atoms to render said compound soluble inhydrocarbons boiling in the gasoline or diesel fuel range;R₂ is analkylene group having 2 to about 8 carbon atoms; R₃, R₄, R₅, R₆, R₇ andR₈ are each independently hydrogen or a lower alkyl group having 1 toabout 4 carbon atoms; R₉ is a straight- or branched-chain alkyl grouphaving 1 to about 10 carbon atoms; m is 0 or 1; n is an integer from 5to 99; and W is a hydroxy(oxypropylene) group having the formula:##STR26## mixtures thereof.
 29. The fuel concentrate according to claim28 wherein said amine moiety is derived from ammonia, a monoamine having1 to about 8 carbon atoms; or a polyamine containing 2 to about 12 aminenitrogen atoms and from 2 to about 40 carbon atoms; R₁ is alkyl having 8to about 120 carbon atoms or alkylphenyl having an alkyl groupcontaining 4 to about 100 carbon atoms; and n is an integer from 10 to50.
 30. The fuel concentrate according to claim 29 wherein R₂ isalkylene having 2 to 4 carbon atoms; R₃, R₄, R₅, R₆, R₇ and R₈ are eachindependently hydrogen, methyl, or ethyl; and R₉ is alkyl having 1 to 6carbon atoms.
 31. The fuel concentrate according to claim 30 whereinsaid amine moiety is derived from a polyalkylene polyamine containing 2to about 12 nitrogen atoms and 2 to about 24 carbon atoms; and R₁ isalkyl having 10 to 30 carbon atoms or alkylphenyl having an alkyl groupcontaining 10 to 30 carbon atoms.
 32. The fuel concentrate according toclaim 31 wherein R₂ is ethylene; R₃, R₄, R₅, R₆, R₇ and R₈ are eachhydrogen; and R₉ is alkyl having 2 to 4 carbon atoms.
 33. The fuelconcentrate according to claim 32 wherein said polyalkylene polyaminehas the formula:

    H.sub.2 N-(R.sub.10 NH).sub.y -H

wherein R₁₀ is alkylene having 2 to about 6 carbon atoms and y is aninteger from 1 to
 3. 34. The fuel concentrate according to claim 33wherein R₁₀ is ethylene.
 35. The fuel concentrate according to claim 34wherein y is 1 or
 2. 36. The fuel concentrate according to claim 28wherein said concentrate contains 10 to 50 weight percent of saidcompound.
 37. The fuel concentrate of claim 28 wherein said concentratecontains about 20 to about 60 weight percent of a fuel-soluble,nonvolatile carrier fluid.